LECTURE 1

CONCENTRATION CHANGE IN A REACTION

As the rate of reaction is dependant on the concentration of reactants... the

forward reaction starts off fast but slows as the reactants get less
concentrated
FASTEST AT
THE START

SLOWS DOWN
AS REACTANTS
ARE USED UP

TOTAL
CONVERSION
TO PRODUCTS

In an ordinary reaction (mostly irreversable); all reactants

end up as products; there is 100% conversion
 EQUILIBRIUM REACTIONS
Initially, there is no backward reaction but, as products form, it speeds up
and provided the temperature remains constant there will come a time when
the backward and forward reactions are equal and opposite; the reaction has
reached equilibrium. FASTEST AT THE START
NO BACKWARD REACTION

FORWARD REACTION SLOWS

DOWN AS REACTANTS ARE
USED UP

BACKWARD REACTION
STARTS TO INCREASE

In an equilibrium reaction, not all the reactants end

up as products; there is not a 100% conversion. AT EQUILIBRIUM THE BACKWARD
AND FORWARD REACTIONS ARE
BUT IT DOESN’T MEAN THE REACTION EQUAL AND OPPOSITE
IS STUCK IN THE MIDDLE
 DYNAMIC EQUILIBRIUM

IMPORTANT REMINDERS
• Reversible chemical reaction is a dynamic process
• Everything may appear stationary but the reactions are moving both ways
• The position of equilibrium can be varied by changing certain conditions

At equilibrium: Rateforward = Ratereverse

A system at equilibrium is dynamic on the molecular level; no further net

change in reactant and product concentrations is observed because changes
in one direction are balanced by changes in the opposite direction and both
the reactants and the products are present at all times
Reaching Equilibrium on the Macroscopic
and Molecular Levels
Example: Equilibrium Established
N2O4(g) 2NO2(g)

N2O4(g) is colorless and NO2(g) is brown

Reach equilibrium
 THE EQUILIBRIUM CONSTANT Kc
for an equilibrium reaction of the form...

aA + bB cC + dD

then (at constant temperature) [C]c . [D]d = (Kc)

[A]a . [B]b

where [ ] denotes the equilibrium concentration in mol dm-3

Kc is known as the Equilibrium Constant
 kforward [products]n (the equilibrium
= = Keq constant)
kreverse [reactants]m

This is also known as the Law of Mass Action.

• forward rate = kf [reactants]m

• reverse rate = kr [products]n
• Kforward : rate constant of reaction in forward direction
• kreverse : rate constant of reaction in backward direction
• The exponents, m and n, are equal to the coefficients in the balanced
chemical equation.
• Note that, The rates of the forward and reverse reactions are equal, not
the concentrations of reactants and products.
 N2O4(g) 2NO2(g)

• The initial concentration of NO2 were

zero, then it increases as the
concentration of N2O4 decreases.
• forward rate = kf [N2 O4 ]
• reverse rate = kr[NO2 ]2
• At equilibrium, the forward reaction rate is
equal to the reverse reaction rate.
kf [N2 O4 ]= kr[NO2 ]2

[NO ]2
kf = 2 eq = K
eq
kr [N2O4]eq
• The equilibrium constant is equal to the rate constant for the forward
reaction divided by the rate constant for the reverse reaction.
 THE EQUILIBRIUM LAW

Simply states
“The product of the concentrations of the products divided by
the product of the concentrations of the reactants at equilibrium
each raised to the power of the number of moles they appear in
the balanced chemical equation is a constant, provided the
temperature remains constant”
Magnitude of the Equilibrium Constant

o If Kc >> 1, products are favored (reaction nearly complete).

o If Kc << 1, reactants are favored (reaction hardly proceeds).
o If Kc is close to 1, the system contains comparable amounts of products and reactants.
 The range of equilibrium constants

small K
nearly all reactant
intermediate K
mix of reactant and
product

large K
nearly all product
There are several forms of the equilibrium constant:

Kc the equilibrium values are expressed as concentrations of mol /L

Kp the equilibrium values are expressed as partial pressure

The partial pressure expression can be used for reactions involving gases
 Gaseous Equilibria Kp

For reactions involving only gases, we can use partial pressures instead of
concentrations to express the equilibrium:

Consider N2O4(g) 2NO2(g)

[NO 2 ] 2 [P N O]2
Kc = KP = 2

[N 2 O 4 ] [P N 2 O 4 ]
Here the “c” stands for concentration; “P” stands for pressure. There is a straightforward
relationship between Kc and KP: From the ideal gas law, applied to an arbitrary species “A”
n
PV = nRT P = VA R T = [A]RT
A
Therefore for N2O4(g) 2NO2(g),
[P N O 2 ]2 [NO 2 ] 2 (RT ) 2
KP = = = Kc(RT )
[PN2O4 ] [N 2 O 4 ](RT )
In general,
K P = Kc(RT )∆n
where n (for gas) = moles of products – moles of reactants.
Problem
For the reaction N2(g) + 3H2(g) 2NH3(g)
Kc = 2.3 x 10-2 at 375°C. Calculate KP at this temperature.

Solution:
∆n
K P = Kc(RT )
and here n = moles of products – moles of reactants
n = 2 – (1 + 3) = 2 – 4 = -2
K P = 2.3 x10-2[0.08206 x (375 + 273)]-2 = 8.1 x 10-6
 Reaction quotient Qc
Reaction quotient Qc is the same expression but without necessarily being at
equilibrium.
In general, for aA + bB cC + dD
[C] c [D] d
Qc =
[A]a [B]b
The Qc expression is also called the law of mass action.

• Using Q and K to Predict the Direction of a Reaction

• by comparing the values of Q and K
 Comparing Q and K to determine reaction direction

Problem For the reaction N2O4(g) 2NO2(g), Kc = 0.21 at 100 oC. At a

point during the reaction, [N2O4] = 0.12 M and [NO2] = 0.55 M. Has
the reaction reached equilibrium? If not, in which direction is it
progressing?
PLAN: Write an expression for Qc, substitute with the values given, and
compare the Qc with the given Kc.

SOLUTION: [NO2] (0.55)2

Qc = 2 = = 2.5
[N2O4] (0.12)

Qc > Kc, therefore the reaction is not at equilibrium and will proceed from
right to left (reverse reaction), from products to reactants, until Qc = Kc.
Problem

At 448°C, KP = 51 for H2(g) + I2(g) 2HI(g)

Predict the direction the reaction will proceed.
the pressures of HI, H2, and I2 are 1.3, 2.1, and 1.7 atm.

Solution:
QP =
P 2 = (1.3)2 = 0.47
HI

P H 2 P I 2 (2.1)(1.7)

The reaction quotient is so the reaction will proceed in the forward direction.
 LE CHATELIER’S PRINCIPLE
”When a change is applied to a system in dynamic equilibrium,
the system reacts in such a way as to oppose the effect of the
change.”
FACTORS AFFECTING THE POSITION OF EQUILIBRIUM:
1. CONCENTRATION
2. PRESSURE
3. TEMPERATURE
4. CATALYST
 FACTORS AFFECTING THE POSITION OF EQUILIBRIUM
1. CONCENTRATION

• The equilibrium constant is not affected by a change in

concentration at constant temperature. To maintain the
constant Kc , the composition of the equilibrium mixture
changes.

• Increasing a reactant concentration → The system shifts

toward products to reduce the added reactant.

• Increasing a product concentration → The system shifts

toward reactants to counteract the change.
 CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)
Problem
the equilibrium constant Kc = [CH3COOC2H5] [H2O] = 4 (at 298K)
[CH3CH2OH] [CH3COOH]
Increasing
[CH3CH2OH] - will make the denominator getting larger so Kc will be smaller
- to keep it constant, some CH3CH2OH reacts with CH3COOH
- this reduces the value of the bottom line and increases the top
- eventually the value of the constant will be restored
Decreasing
[H2O] - will make the numerator getting smaller
- some CH3CH2OH reacts with CH3COOH to replace the H2O
- more CH3COOC2H5 is also produced
- this reduces the value of the bottom line and increases the top
 Initial concentration (M) Concentrations at
Exp. Equilibrium
[N2 O4 ] (M) [NO2 ] (M) [N2 O4 ] (M) [NO2 ] (M) [NO2 ]2
K=
[N2 O4 ]
1 0.0500 0.0000 0.0417 0.0165 6.54 × 10−3
2 0.0000 0.1000 0.0417 0.0165 6.54 × 10−3
3 0.0750 0.0000 0.0647 0.0206 6.56 × 10−3
4 0.0000 0.0750 0.0304 0.0141 6.54 × 10−3
5 0.0250 0.0750 0.0532 0.0186 6.50 × 10−3

• VALUE OF Kc NOT AFFECTED by a change in concentration of reactants or products

 FACTORS AFFECTING THE POSITION OF EQUILIBRIUM

SUMMARY

REACTANTS PRODUCTS
THE EFFECT OF CHANGING THE CONCENTRATION ON THE POSITION OF
EQUILIBRIUM
INCREASE CONCENTRATION OF A EQUILIBRIUM MOVES TO THE
REACTANT RIGHT
DECREASE CONCENTRATION OF A EQUILIBRIUM MOVES TO THE
REACTANT LEFT
INCREASE CONCENTRATION OF A EQUILIBRIUM MOVES TO THE
PRODUCT LEFT
DECREASE CONCENTRATION OF A EQUILIBRIUM MOVES TO THE
PRODUCT RIGHT
 Problem
2SO2(g) + O2(g) 2SO3(g)

• Predict the effect of increasing the concentration of O2 on the

equilibrium position

EQUILIBRIUM MOVES TO Right (Forward Direction)

• Predict the effect of decreasing the concentration of SO3 on the

equilibrium position

EQUILIBRIUM MOVES TO Right (Forward Direction)